Glass ceramic dielectric material suitable for production of a microwave circuit component

ABSTRACT

Glass powder for a dielectric material has a nature that, when fired, diopside (CaMgSi 2 O 6 ) and at least one of titanite (CaTi(SiO 4 )O) and titania (TiO 2 ) are precipitated. Preferably, the glass powder has a composition including SiO 2 , CaO, MgO, and TiO 2  and the total content of these components is 80 mass % or more. Preferably, the glass powder comprises, by mass percent, 35–65% SiO 2 , 10–30% CaO, 10–20% MgO, and 12–30% TiO 2 .

CROSS REFERENCE TO RELATED APPLICATIONS

This is a divisional of application Ser. No. 10/379,181, filed on Mar.4, 2003, now U.S. Pat. No. 6,875,715. Applicants claim priority under 35U.S.C. 119 of Japanese application Serial No. 57236/2002, filed on Mar.4, 2002.

BACKGROUND OF THE INVENTION

This application claims priority to Japanese Patent Application No.2002-57236, disclosure of which is incorporated herein by reference.

The present invention relates to a glass ceramic dielectric materialsuitable for production of a microwave circuit component.

As a material of a circuit component, such as a ceramic substrate, towhich ICs or LSIs are mounted at a high density, use is made of analumina ceramic material and a glass ceramic material including glasspowder and ceramic powder. In particular, the glass ceramic material canbe fired at a temperature not higher than 1000° C. although it isinferior in mechanical strength to the alumina ceramic material.Therefore, the glass ceramic material is advantageous in that thematerial can be co-fired with Ag, Cu, or the like low in conductorresistance.

In recent years, remarkable development has been achieved in the fieldsof a mobile communication apparatus, such as a mobile telephone and apersonal radio equipment, and a new media apparatus used in a new media,such as satellite broadcasting, satellite communication, and CATV. Inthe mobile communication apparatus and the new media apparatus, amicrowave circuit component is used. It is required that the microwavecircuit component is made of a material low in dielectric loss in ahigh-frequency region not lower than 0.1 GHz.

Sometimes, the microwave circuit component itself is required to serveas a resonator. In this case, the material of the microwave circuitcomponent is required to have temperature stability, i.e., to beunchanged in resonance frequency depending upon the temperature.

For example, Japanese Unexamined Patent Publication No. H10-120436 (JP10-120436 A) proposes a glass ceramic material which precipitatesdiopside crystals. By the use of the glass ceramic material, it ispossible to obtain a sintered product low in dielectric loss in thehigh-frequency region. However, the glass ceramic material has adielectric constant between 6 and 8, which is lower than that ofalumina. In addition, the glass ceramic material is inferior intemperature stability because a temperature coefficient of the resonancefrequency is −65 ppm/° C.

SUMMARY OF THE INVENTION

It is therefore an object of the present invention to provide a glassceramic dielectric material which is capable of producing a sinteredproduct having a dielectric constant equivalent to that of alumina andis excellent in temperature stability.

It is another object of the present invention to provide a glass ceramicdielectric material of the type described, which is capable of producinga sintered product being low in dielectric loss at a frequency in amicrowave region.

It is still another object of the present invention to provide a glassceramic dielectric material of the type described, which is capable ofproducing a sintered product having a near-zero temperature coefficientof a resonance frequency.

It is yet another object of the present invention to provide a glassceramic dielectric material of the type described, which is capable ofbeing fired at a temperature not higher than 1000° C. to produce any ofthe sintered products.

Other objects of the present invention will become clear as thedescription proceeds.

As a result of extensive studies, the present inventors have found outthat the dielectric constant equivalent to that of alumina and thenear-zero temperature coefficient of the resonance frequency aresimultaneously achieved by precipitation of at least one of titanite andtitania in addition to diopside.

According to an aspect of the present invention, there is provided glasspowder for a dielectric material, which has a nature that, when fired,diopside (CaMgSi₂O₆) and at least one of titanite (CaTi(SiO₄)O) andtitania (TiO₂) are precipitated.

According to another aspect of the present invention, there is providedglass powder for a dielectric material, which comprises, by masspercent, 35–65% SiO₂, 10–30% CaO, 10–20% MgO, and 12–30% TiO₂.

According to still another aspect of the present invention, there isprovided a glass ceramic sintered product which includes, asprecipitated crystals, diopside (CaMgSi₂O₆) and at least one of titanite(CaTi(SiO₄)O) and titania (TiO₂).

According to yet another aspect of the present invention, there isprovided a microwave circuit component comprising a dielectric layer ofa glass ceramic sintered product which includes, as precipitatedcrystals, diopside (CaMgSi₂O₆) and at least one of titanite(CaTi(SiO₄)O) and titania (TiO₂).

DESCRIPTION OF THE PREFERRED EMBODIMENT

Now, description will be made of a glass ceramic dielectric materialaccording to an embodiment of the present invention.

Preparation is made of a glass ceramic dielectric material which, whenfired, produces a glass ceramic sintered product containing, asprecipitated crystals, not only diopside having a low dielectric lossbut also titanite (CaTi(SiO₄)O) and/or titania (TiO₂) high in dielectricconstant than diopside. In other words, the glass ceramic dielectricmaterial has ability of precipitating diopside and titanite and/ortitania. By precipitation of these crystals, i.e., titanite and/ortitania, in addition to diopside, the dielectric constant and thedielectric loss of the resultant glass ceramic sintered product in ahigh-frequency region not lower than 0.1 GHz can be adjusted to 9–10 and20 or less, respectively.

The amount of the precipitated crystals can be controlled by the contentof TiO₂. For example, if it is desired to inrease the amount of theprecipitated crystals, the content of TiO₂ is increased.

In order to precipitate the crystals, use is made of crystallizableglass powder including SiO₂, CaO, MgO, and TiO₂ as main components sothat the total content of these main components is 80 mass % or more,preferably 90 mass % or more. If the total content of the maincomponents is smaller than 80 mass %, it is often that heterogeneous ordifferent crystals are precipitated or desired crystals are notprecipitated. It is desired to use a glass comprising, by mass %, 35–65%SiO₂, 10–30% CaO, 10–20% MgO, and 12–30% TiO₂.

Next, description will be made of a composition range of the glasspowder.

SiO₂ serves as a network former of the glass and as a component ofdiopside and titanite. The content of SiO₂ is 35–65%, preferably 40–55%.If the content of SiO₂ is smaller than 35%, vitrification is difficult.On the other hand, if the content is greater than 65%, firing at atemperature not higher than 1000° C. is difficult. This makes itdifficult to use Ag or Cu as a conductor or an electrode.

CaO is a component of diopside and titanite. The content of CaO is10–30%, preferably 15–25%. If the content of CaO is smaller than 10%,these crystals are hardly precipitated so that the dielectric loss isincreased or the dielectric constant is not increased. If the content isgreater than 30%, vitrification is difficult.

MgO is a component of diopside. The content of MgO is 10–20%, preferably12–17%. If the content of MgO is smaller than 10%, precipitation ofcrystals is difficult. If the content is greater than 20%, vitrificationis difficult.

TiO₂ is a component to increase the dielectric constant of the glass aswell as a component of titanite and titania. The content of TiO₂ is12–30%, preferably 15–27%. If the content of TiO₂ is smaller than 12%,precipitation of titanite and/or titania is difficult and the dielectricconstant is not sufficiently increased. In addition, the temperaturecoefficient of the resonance frequency is lower than −10 ppm/° C. If thecontent is greater than 30%, the dielectric constant becomes excessivelyhigh. Simultaneously, the temperature coefficient of the resonancefrequency is higher than 10 ppm/° C.

In addition to the above-mentioned components, other components may beadded as additional components as far as electrical characteristics suchas the dielectric constant and the dielectric loss are not degraded. Forexample, in order to improve meltability, 10% or less SrO and/or 10% orless BaO may be added. In order to improve chemical durability, 10% orless ZrO₂ may be added. It is desired that the total content of theseadditional components is restricted to be smaller than 20%.

The glass ceramic dielectric material may comprise the above-mentionedglass powder alone. Alternatively, for the purpose of improvingmechanical characteristics such as bending strength and toughness of theresultant sintered product, the glass powder may be mixed with ceramicpowder. In this case, the amount of the ceramic powder to be mixed ispreferably not greater than 50 mass %. This is because a dense andcompact structure is difficult to obtain if the amount of the ceramicpowder exceeds 50 mass %.

Preferably, the ceramic powder has a dielectric constant of 16 or lessand a dielectric loss not greater than 10×10⁻⁴ in a frequency regionbetween 0.1 and 10 GHz. For example, use may be made of alumina,cristobalite, forsterite, zircon, and zirconia. If the dielectricconstant of the ceramic powder exceeds 16, the dielectric constant ofthe glass ceramic sintered product tends to become high. If the ceramicpowder has a dielectric loss exceeding 10×10⁻⁴ in a frequency regionbetween 0.1 and 10 GHz, the dielectric loss of the glass ceramicsintered product is increased.

The glass ceramic dielectric material described above can be fired at alow temperature not higher than 1000° C. Therefore, Ag or Cu low inconductor resistance can be used as a conductor.

Next, description will be made of a method of producing a circuitcomponent by the use of the above-mentioned glass ceramic dielectricmaterial.

At first, preparation is made of glass powder or mixed powder of glasspowder and ceramic powder. To the glass powder or the mixed powder, abinder, a plasticizer, and a solvent in predetermined amounts are addedto prepare a slurry. For example, the binder may be polyvinylbutyralresin or methacrylate resin. The plasticizer may be dibutyl phthalate.The solvent may be toluene or methyl ethyl ketone.

Then, the slurry is formed into a green sheet by the doctor blademethod. Thereafter, the green sheet is dried or dehydrated, cut into apredetermined size, and subjected to mechanical working to form viaholes. A low-resistance metal material to serve as a conductor or anelectrode is filled in the via holes and deposited on the surface of thegreen sheet. Then, a plurality of similar green sheets are laminated andintegrated by thermocompression bonding.

Next, the green sheets thus laminated are fired to obtain a glassceramic sintered product. The sintered product thus produced has theconductor and the electrode in the interior or on the surface thereof.Preferably, the firing temperature is not higher than 1000° C., moreparticularly, 800–950° C.

The glass ceramic sintered product thus obtained has a dielectricconstant between 9 and 10, which is approximate to that of alumina.Therefore, in case where the glass ceramic sintered product is usedinstead of alumina, it is unnecessary to widely change a circuit design.Furthermore, since the glass ceramic sintered product has a lowdielectric loss and a near-zero temperature coefficient of a resonancefrequency in a high-frequency region not lower than 0.1 GHz, the glassceramic sintered product is suitable for use as a microwave circuitcomponent.

A chip or chips of Si-based or GaAs-based semiconductor devices areconnected to the glass ceramic sintered product produced in the mannerdescribed above. Thus, a microwave circuit component having a dielectriclayer of the glass ceramic sintered product is obtained.

In the foregoing, the green sheet is used for production of the glassceramic sintered product. However, without being restricted thereto, usemay be made of various other methods generally used for production ofceramic.

Hereinafter, several specific examples of the present invention will bedescribed together with a comparative example.

Tables 1 and 2 show the specific examples (Samples Nos. 1–6) of thepresent invention and the comparative example (Sample No. 7).

Each sample was prepared in the following manner.

At first, a glass material having each composition in Tables wasprepared. Thereafter, the glass material was put into a platinumcrucible, melted at 1400 to 1500° C. for 3 to 6 hours, and formed by awater-cooled roller into a formed product in the shape of a thin plate.Then, the formed product was coarsely pulverized and then subjected towet grinding by a ball mill with alcohol added thereto. Thus, glasspowder having an average particle size of 1.5 to 3.0 μm was obtained.For each of Samples Nos. 2 to 6, the ceramic powder (having an averageparticle size of 2 μm) shown in Tables was added to the glass powder toobtain mixed powder.

TABLE 1 Sample 1 2 3 4 Glass Composition (mass %) SiO₂ 48 45 37 42 CaO20 19 24 25 MgO 15 14 17 16 TiO₂ 17 22 20 25 SrO — — 2 — ZrO₂ — — — 2BaO — — — — Ceramic Powder species — alumina forsterite cristobaliteratio (mass %) — 40 30 35 Firing Temperature (° C.) 880 900 890 900Precipitated Crystals diopside diopside diopside diopside titanitetitanite titanite titanite titania titania titania titania (rutile)(rutile) (rutile) (rutile) Dielectric Constant 9.6 9.3 9.2 9.8Dielectric Loss (×10⁻⁴) 15 11 13 15 Temperature Coefficient of −5 3 2 7Resonance Frequency (ppm/° C.)

TABLE 2 Sample 5 6 7 Glass Composition (mass %) SiO₂ 43 51 50 CaO 27 2030 MgO 13 12 20 TiO₂ 15 17 — SrO — — — ZrO₂ — — — BaO 2 — — CeramicPowder species zircon zirconia alumina ratio (mass %) 25 30 40 FiringTemperature (° C.) 890 900 900 Precipitated Crystals diopside diopsidediopside titanite titanite titania (rutile) Dielectric Constant 9.7 9.57.8 Dielectric Loss (×10⁻⁴) 14 11 8 Temperature Coefficient of −7 −6 −65Resonance Frequency (ppm/° C.)

For each of the powder samples thus obtained, the firing temperature,the precipitated crystals, the dielectric constant, the dielectric loss,and the temperature coefficient of resonance frequency were measured.

As seen from Tables, it has been confirmed that each of Samples 1 to 6can be fired at a low temperature between 880 and 900° C. and, afterfiring, contained titanite crystals and/or titania crystals precipitatedtherein in addition to diopside crystals. At a frequency of 2.4 GHz,each of Samples 1 to 6 had a dielectric constant between 9.2 and 9.8,which is equivalent to that of alumina, and a small dielectric loss.Furthermore, the temperature coefficient of the resonance frequency was−7 to 7 ppm/° C., which is a near-zero value. On the other hand, SampleNo. 7 had a low dielectric constant of 7.8. The temperature coefficientof the resonance frequency was −65 ppm/° C., which is apart from zero.

The firing temperature was determined as follows. To the sinteredproducts fired at various temperatures, ink was applied and then wipedoff. Among those samples which had no residue of ink (i.e., which wasdensely sintered), one sample fired at a lowest temperature wasselected. The lowest temperature was used as the firing temperature.

The precipitated crystals were identified by the X-ray diffractionanalysis after each sample was fired at the temperature shown in Tables.

The dielectric constant and the dielectric loss were measured by the useof the fired sample. The values at a temperature of 25° C. were obtainedby the use of a cavity resonator (at the measurement frequency of 2.4GHz).

The temperature coefficient of the resonance frequency was obtained forthe fired sample in accordance with Japanese Industrial Standard JISR1627 (at the resonance frequency of 15 GHz).

1. A glass ceramic sintered product which includes, as precipitatedcrystals, diopside (CaMgSi₂O₆) and at least one of titanite(CaTi(SiO₄)O) and titania (TiO₂).
 2. A microwave circuit componentcomprising a dielectric layer of a glass ceramic sintered product whichincludes, as precipitated crystals, diopside (CaMgSi₂O₆) and at leastone of titanite (CaTi(SiO₄)O) and titania (TiO₂).